Production of metamjg driers



latentecl Dec. 21, 1937 PATENT OFFICE PRODUCTION OF META-LIiIG DRIERS-Kenneth E. Long, South Euclid, Ohio, assignor to The Harshaw ChemicalCompany, Elyria, Ohio, a corporation of Ohio No Drawing. ApplicationNovember 10, 1933, Serial No. 697,472

12 Claims. (Cl. 134- 57) This invention relates to driers for use inpaintsvarnishes, printing inks, etc. and it is among the objects of theinvention to provide improved driers of high metallic content and 5controlled acidity or basicity. A further object is the provision of aconvenient and effective manufacturing procedure for making acid,neutral or basic driers containing one or more metals. Other objects andadvantages will appear as the description proceeds.

acid type is modified by an agent providing an organic carboxyl acidradical reactive therewith, and thus which may be an organic acid, aneutral or acid lead salt of an organic acid, or a neutral or acidorganic salt of a drier metal, such as cobalt, manganese, zinc. Forinstance, as the basic lead salt there may be employed a metallic saltwhich is prepared by intimately mixing and reactin'g between lead oxide,PbO, and a fatty acid such as linseed fatty acid, an acid derived frompetroleum, as naphthenic acids, synthetic fatty acids made by theoxidation of petroleum hydrocarbons, etc., the formation of the leadsalt being carried out at temperatures below 100 C., and with finaldriving off of reactionwater by raising the temperature, for instance to100200 C. To such a basic salt there is added, with intimate.incorporation, a modifying substance of the types mentioned. Advantageis taken of the basic character of the lead salt to accomplish theformation of desirable properties in each case. For instance, a basiclead salt of high metallic content may be modified by mixture andreaction with rosin acids to form a less basic, neutral or acid drierwith varying physical characteristics. For certain purposes, such asprinting ink driers, it is of particular advantage to thus be able tovary the viscosity and penetration of the drier. Such modification of abasic drier allows combinations impossible to achieve by mixtures ofneutral or acid driers.

If instead of using rosin, a fused acid lead resinate is mixed andreacted with a'basic lead drier, it is possible to obtain a neutral,basic or slightly acid drier with high metallic content and a highproportion of the cheap rosin acids. As it is extremely difiicult toprepare a neutral lead resinate by the old fusion process, thisprocedure furnishes a convenient method of preparing and controllingtheacidity of compounds which may be used in the place of lead resinate.

Ordinary cobalt, manganese and zinc driers heretofore known oftenrequire free organic acid to keep them in solution in paint solvents.But free acid inhibits the drying of the paint film. In the presentinvention, by mixing and reacting a neutral or acid salt of this kindwith a basic lead drier, the resulting combined drier, even thoughbasic, is perfectly stable in paint solvents, and due to the lack offree acid is a more eflicient drier. I

The practice of the invention may be carried out in several convenientways. For example, the basic lead drier may be melted together with themodifying substance. If the modifying substance is an acid or containsfree acid, water is formed by the reaction with the basic lead and isremoved by heating. Thus it is possible to make basic, neutral orslightly acid mixed driers from the cheaper but highly acid fused saltsof cobalt, manganese and zinc. Again, a mixed drier may beadvantageously prepared by incorporating the cobalt, manganese or zineeither as neutral or acid organic salts or directly as hydrate orcarbonate, into the organic acid used to make the basic lead salt. Thissolution of metallic drier in organic acid is used exactly as if it wereall acid and is mixed in the usual manner with litharge to form a basiclead salt.

Examples illustrative of the invention may be noted as follows:

I. About parts of synthetic fatty acids made by the oxidation ofpetroleum hydrocarbons, and having an acid value of about 360, arethoroughly mixed with about parts of lead oxide, PbO', advantageously bygrinding on an ink mill, the temperature being maintained below 100 C.for reaction, and then finally being raised to above 100 C. to drive offwater of reaction. The highly basic lead salt so formed is thenthoroughly mixed by melting with 30 per cent of itsweight of rosin. Thelead salt resultant is a combination with synthetic fatty acids androsin acids, the basicity of the primary lead fatty acid compoundsrbeingmodified, and the product containing about 40 per cent of lead, andbeing soluble in paint solvents, such as mineral spirits, xylol, etc.,and also in linseed oil.

II. In the above example there is added instead of rosin, a highly acidlead resinate containing approximately 16 per cent lead in the amount oftwice the weight of the basic lead salt. An ap-- proximately neutralmixed salt is formed, containing a high percentage of rosin and about 28per cent lead. This mixed salt may be used in place of fused leadresinate as a drier, and is far superior in drying qualities andstability in solvents.

III. About 25 parts of cobalt naphthenate com A taining 3 parts ofcobalt are mixed by melting together with parts of a highly basic leadnaphthenate containing 30 parts of lead. The resulting product is ahighly basic mixed drier containing 3 per cent cobalt and 30 per centlead which is perfectly stable in paint solvents and is a highlyefficient drier.

I do not of course limit myself to these proportions or procedures, butgive these examples as illustrations of the modification of a basic leaddrier to produce a product of high metallic content and controlledacidity or basicity. Cobalt, manganese and zinc may be used in anyproportion either singly or together with any amount of free acid, tomodify the basicity of a basic lead drier to obtain new and efiicientpaint or varnish driers.

Other modes of applying the principle of the invention may be employed,change being made as regards the details described, provided thefeatures stated in any of the following claims, or the equivalent ofsuch, be employed.

I therefore particularly point out and distinctly claim as my invention:

1. A process of making driers, which comprises preparing a basic leaddrier salt, and controllably lessening the basicity of the basic salt byreacting on the basic salt with an agent providing an organic carboxylacid radical reactive therewith the resulting drier being basic but oflesser basicity than the basic lead drier salt initially treated.

2. A process of making driers, which comprises preparing a basic leaddrier salt, and controllably lessening the basicity of the basic salt byreacting on the basic salt with an organic carboxyl acid reactivetherewith the resulting drier being basic but of lesser basicity thanthe basic lead drier salt initially treated.

3. A process of making driers, which comprises lessening the basicity ofa basic lead drier salt by reacting thereon with resin acid theresulting drier being basic but of lesser basicity than the basic leaddrier salt initially treated.

4. A process of making driers, which comprises lessening the basicity ofa basic lead drier salt of a petroleum-derived acid by reacting thereonwith resin acid the resulting drier being basic but of lesser basicitythan the basic lead drier salt initially treated.

5. A process of making driers, which comprises lessening the basicity ofa basic lead drier salt of fatty acids oxidized from petroleum byreacting thereon with resin acid the resulting drier being basic but oflesser basicity than the basic lead drier salt initially treated.

6. A process of making driers, whichcomprises lessening the basicity ofa basic lead drier salt of napthenic acids by reacting thereon withresin acid the resulting drier being basic but of lesser basicity thanthe basic lead drier salt initially treated.

'7. A drier compound, comprising a basic lead drier salt having itsbasicity lessened by resin acid the resulting drier being basic but oflesser basicity than the basic lead drier salt initially treated.

8. A drier compound, comprising a basic lead drier salt of apetroleum-derived acid having its basicity lessened by resin acid theresulting drier being basic but of lesser basicity than the basic leaddrier salt initially treated.

9. A drier compound, comprising a basic lead drier salt of fatty acidsoxidized from petroleum having its basicity lessened by resin acid theresulting drier being basic but of lesser basicity than the basic leaddrier salt initially treated.

10. A drier compound, comprising a basic lead drier salt of naphthenicacids having its basicity lessened by resin acid the resulting drierbeing basic but of lesser basicity than the basic lead drier saltinitially treated.

11. A drier compound, comprising a basic lead drier salt having itsbasicity lessened by an agent providing an organic carboxyl acid radicalreactive therewith the resulting drier being basic but of lesserbasicity than the basic lead drier salt initially treated.

12. A drier compound, comprising a basic lead driersalt having itsbasicity lessened by an organic carboxyl acid reactive therewith theresulting drier being basic but of lesser basicity than the basic leaddrier salt initially treated.

KENNETH E. LONG.

